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NANOMATERIALS: APPLYING THE PRECAUTIONARY PRINCIPLE

Photo credit: Hinkle Group, licensed under CC BY-NC-SA 2.0 Nanomaterials: Applying the Precautionary Principle

Nanodimensions – New discoveries about Nanomaterials are composed of nanosized particles, familiar materials measuring less than 100 nanometres in at least one dimension: a nanometre is one-billionth of a metre, or roughly 80 000 The 2016 Nobel Prize in Chemistry was awarded to Jean- times smaller than a human . Nanomaterials are not new Pierre Sauvage, Sir J. Fraser Stoddart and Bernard L. Feringa and they are not all synthetic; they do occur naturally and they for their three decades of learning to design and synthesize are everywhere. What is new is our ability to engineer them molecular , demonstrated by a four-nanometre- from common materials for a functional purpose. long ‘car’ with four wheels operated by molecular motors.1 Scientists have continued to push the boundaries and explore In the natural world, nanomaterials appear in the skeletons of new , in this case for innovations beyond physical marine plankton and ; bird and ; animals’ limitations that realize the potential for countless applications hair and matrix, including the human variety; spider webs; in everyday life. The recent advances in scales and wings; even in , silk and . There are also and nanoscience have introduced nanoscale materials naturally occurring inorganic nanomaterials, such as some with emergent physical and chemical properties to clays, volcanic ash, soot, interstellar dust, and certain minerals. transform the world.2,3,4 Natural nanomaterials are fundamentally a result of chemical, photochemical, mechanical, thermal and biological processes.5,6

24 Research suggests that some preparation methods used in traditional medicine, such as calcination, inadvertently produce nanomaterials and their particular attributes.7,8 Natural Manufactured As well, researchers are examining medieval weapons, such as Damascus steel blades, to test the theory that specific 1 millimetre (mm) and ritualized forging and annealing techniques exploited production of nanomaterials to enhance strength and 9,10 A grain of sand suppleness of the steel. 1 mm

100 micrometre (μm) Paper thickness In the engineered world, nanomaterials are deliberately or micron 100 μm designed and synthesized for specific optical, electronic, mechanical, medical and enzymatic applications using Human hair a range of micro-fabrication techniques. Today, nanomaterials 80 μm are widely used in a variety of products, such as food, Glass fibre optic cosmetics, personal care products, agents 10 micron 50 μm and disinfectants, clothing and electronic devices. Along FACIAL SCRUB with the excitement about opportunities the engineered Fern spores nanomaterials could present, questions have emerged about 50 μm the environmental safety of nanomaterials, as well as their microbeads in facial scrubs production and applications. There are still significant gaps in 1 micron = 1-1 000 μm 1 000 nanometre (nm) our knowledge about what nanomaterials could do and what effects they might have. Despite many more nanomaterials Spider silk being developed, there is a serious risk that we do not know 4 μm enough about the long-term effects of these materials on Nanosilica used as food additive human health or the environment to use them without 100 nm 10-200 nm greater safeguards in place. Ebola virus 80 nm

10 nm Quantum dots or Nanocrystaline, used in ultra-efficient solar cells 2-10 nm fibrils 25 nm

1 nm Nanomachine The creators won the 2016 Nobel Prize nanotube DNA diameter in Chemistry diameter 4 nm 2.5 nm 1 nm

H 0.1 nm O H

Buckminsterfullerene C60 or buckyball Water 0.7 nm 0.27 nm Nanosized wing scale of Cabbage White Butterfly, Pieris brassicae

Photo credit: ZEISS Microscopy, licensed under CC BY-NC-ND 2.0 REPORT 2017 FRONTIERS ENVIRONMENT UN

25 NANOMATERIALS: APPLYING THE PRECAUTIONARY PRINCIPLE

Specific forms, applications and effects

In Lewis Carroll’s story of Alice’s Adventures in Wonderland, young Alice swallows a potion that makes her very small. In her new size, she is able to enter a world of animals and characters that have extraordinary behaviours quite unlike their larger world versions. At nanoscale, the physical, chemical, optical, magnetic and electrical properties and behaviours of the materials change significantly compared to the same materials at larger sizes. This happens because of the dramatic increase in the surface-to-volume ratio and the appearance of quantum effects as a material gets smaller. Rendering a nanosized version of a material can produce capabilities in materials that are otherwise inert. For example, bulk gold is diamagnetic—it responds very weakly

to magnetic field—but gold possess unusual Iron (III) oxide (Fe2O3) , grown on reduced oxide for magnetic properties.11 supercapacitors Photo credit: Dilek Ozg/Engineering at Cambridge, licensed under CC BY-NC-ND 2.0 Like their bulk counterparts, nanoforms of metals, such as silver, titanium and zinc and their oxides, are used in Nanodiamonds demonstrate functional characteristics that sunscreen, toothpaste, cosmetics, food, paints, and clothing.12 enable them to penetrate through the -brain barrier, Due to its antimicrobial properties, nanosilver is widely and allow targeted delivery of remedies to multiple types incorporated into many consumer products such as sports of cancerous tumours.13,14 Because of their , textiles, shoes, deodorants, personal care items, washing optical and electrochemical properties, nanodiamonds are powder and washing machines. used in advanced bioimaging techniques, and promising materials for transmitting signals that indicate the health of brain function.15,16

Nanozymes are nanomaterials with intrinsic enzyme-like properties developed for biosensing, bioimaging, tumour diagnosis and therapy.17 They also find applications in marine anti-fouling, pollutant removal and environmental monitoring.

Carbon nanomaterials can present themselves in various shapes and forms. Graphene is a single--thick sheet of carbon. Carbon nanotubes are essentially graphene sheets rolled into seamless hollow cylinders with diameters of the order of a nanometre.18 Discovered in 1985, , or buckyball, is a spherical structure of 60 carbon , named after R. , famous for his design of geodesic domes.

Aluminium oxide (Al2O3) nanospheres Photo credit: ZEISS Microscopy licensed under CC BY-NC-ND 2.0

26 Nanomaterials

Applications What is a Nanomaterial? Nanomaterial is a material with any external The unique mechanical, dimension measured magnetic, electrical and less than optical properties of Cu 100 nanometres—one nanomaterials provide endless nanometre is one-billionth applications in pharmaceutical, Ti Au Zn Ag of a metre biomedical, electronic and material Nanomaterials can be Engineered nanomaterials Nanosilver engineering naturally occurring, or is widespread in products, such as are present in diverse fabricated by scaling textiles, toys, personal and health consumer items, e.g. food commonly used materials to care products, medical devices products, cosmetics, nanosize, such as carbon, and food, owing to its disinfectants, kitchenware, metal oxides and antimicrobial baby goods, clothing, precious metals Global properties fabrics, electronics Nanomaterials market Because of its magnetic properties, and appliances iron oxide nanoparticles 20.7% Annual Growth have great potentials for targeted At nanoscale, the in properties and Projected to reach treatment, medical imaging behaviours of a US$ 55 billion techniques, and removal of material change significantly by 2022 arsenic from water compared to the bulk forms of Nanodiamond Graphene is a single-atom- the same material. This is is used in biomedical thick sheet of carbon atoms. imaging applications due due to the increase in the Bulk material Nano-sized material Potential applications include surface-to-volume to its luminescent properties, drug delivery systems, high chemical stability ratio and the molecular transporters, and biocompatibility quantum effects. A football-like cage of As material size decreases, surface area-to-volume 60 carbon atoms, known as and implants. ratio increases, making the material more Buckminsterfullerene chemically reactive to its surrounding environment (C60) or buckyball, has potentials for the treatment of bone and cartilage degeneration, and The miniscule musculoskeletal and bone dimensions and high marrow disorders surface-to-volume ratio that is a one- give engineered nanomaterials atom thick layer of carbon rolled remarkable properties also alter up into a seamless cylinder. It is how they interact with and 117 times stronger than steel accumulate in biological systems, of the same diameter and ranging from the environment, a better conductor living organisms, organs, ! than . cells, down to the DNA level If we want to realise the full potential of engineered Changing the properties of a For example, nanomaterials, we must also material by nanosizing it can carbon nanotubes look anticipate their impacts, Carbon nanotubes are widely intensify its health and behave like asbestos otherwise we risk exposing used in lithium ion batteries, and environmental fibres. Their long and pointy ourselves to far greater lightweight wind turbine impacts structure can pierce through tissue, impacts in the future Iterative and responsive blades and data cables. and cause inflammation and fibrosis regulatory frameworks that Potential applications include much like the effects of asbestos apply the precautionary tissue engineering and exposure. Nanosilver can disturb principle are needed to regeneration, and cancer REPORT 2017 FRONTIERS ENVIRONMENT UN the immune system, and cause minimize the risks and ensure biomarker. Adverse Effects abnormality in gene human health and 27 expression environmental safety NANOMATERIALS: APPLYING THE PRECAUTIONARY PRINCIPLE

Carbon nanotubes have amazing properties. They are stronger than steel, are better conductors than copper, and have higher thermal conductivity than diamonds. Carbon nanotubes are widely used in lithium ion batteries for notebook computers and mobile phones, lightweight wind turbine blades, boat hulls, data cables, and and medical devices.19 The worldwide commercial production capacity of carbon nanotubes now exceeds several thousand tons per year.

As engineered nanomaterials replace more conventional materials in everyday products, it is vital that we know the adverse effects of such materials. If we want to realise the full potential of nanomaterials, we must also anticipate their environmental and human health impacts; otherwise we risk exposing ourselves to far greater risks in the future.20

Changing the properties of a material by nanosizing it can Carbon nanotubes being spun to form a yarn intensify its environmental and health impacts. In the case Photo credit: Commonwealth Scientific and Industrial Research Organisation (CSIRO) of nanosilver, its toxicity can cause argyria, which turns the Video: Graphene - the material of the future permanently into a metallic blue colour; pulmonary ; alterations in organ functions and disturbances to the immune system and gene expression.12,21,22 Exposure to silver nanoparticles can produce a stress response and genomic changes in , which may contribute to the development of genes.12,23 Silicon and titanium dioxides can cause pulmonary inflammation.24

In parallel to the continuing discoveries of novel biomedical

and therapeutic applications of , including C60 buckyballs, these incredible nanomaterials are also under investigation for their potential effects on cells, gene expression, immune function, metabolism and fertility.25 Carbon nanotubes and carbon nanofibres demonstrate their ability to cause damage to skin, eye, lung and brain tissues, and accumulate in the body.26,27

Video link: https://www.youtube.com/watch?v=TFo2xShvtj0 © DW Tomorrow Today Photo credit: Olive Tree/Shutterstock.com

28 Environmental and health exposure to In contrast, knowledge and evidence of the toxicity effects engineered nanomaterials of nanomaterials is expanding. Results suggest that nanomaterials can cause a wide range of adverse health The global nanotechnology market is projected to grow roughly effects. Comparative toxicity studies of familiar materials, 18 per cent per year and be worth nearly US$174 billion by particles and fibres with shape and chemical characteristics 2025.28 The increased production and use of engineered similar to those of nanomaterials, such as asbestos, nanomaterials by diverse industries will likely result in their ultra-fine particles and diesel exhaust fumes, provide unintentional release into the environment at any point insights into the potential health threats from being along the product’s lifecycle.29 For example, nanosilver from exposed to nanomaterials.37 Further, what we have learned clothing and fabric is released during washing; from managing these well-known hazardous substances nanoparticles in paint and building materials are emitted to could also help us to better prepare for the less understood the air and water due to weathering; and carbon nanotubes nanomaterials. become airborne during production or leach from discarded lithium-ion batteries into soil and groundwater.19,30,31 Carbon nanotubes are found to share similar characteristics with asbestos fibres.38 They have needle-like shape, and To assess the potential human health and environmental both are biopersistent. They can pierce through lung tissue risk, it is critical to understand the exposure and adverse and cause inflammation.39 Evidence of the health hazard of effects of engineered nanomaterials.32 At present, a limited working with asbestos came as early as 1898 from Lucy Deane, number of studies are available to explain the fate of one of the first women Inspectors of Factories in the UK.40 engineered nanomaterials once released into the atmosphere, She noted that asbestos work was a ‘demonstrated danger soil, sediment, water and biota, including their behaviour, to the health of workers ... because of ascertained cases of concentration, transport, distribution, transformations, injury to bronchial tubes and lungs medically attributed to the bioavailability, bioaccumulation in food chains, and employment of the sufferer’. biochemical interactions with ecological communities.29,33-36

Aligned carbon nanotubes Asbestos fibres magnified 1500 times under scanning electron

Photo credit: Junbing Yang/Argonne National Laboratory, licensed under CC BY-NC-SA 2.0 Photo credit: US Centers for Disease Control and Prevention/ John Wheeler/ Janice Haney Carr REPORT 2017 FRONTIERS ENVIRONMENT UN

29 NANOMATERIALS: APPLYING THE PRECAUTIONARY PRINCIPLE

Appropriate regulations for health and environmental safety

From our experience with asbestos and other hazardous materials, we know the list of potential threats is long. Environmental exposure of engineered nanomaterials is inevitable. Their adverse effects and persistence could have significant consequences on organisms, ecosystems and food chains.32,35,43,44 Oral, dermal and pulmonary exposure could lead to inflammation and fibrosis, disrupt metabolism and organ’s function, and induce DNA damage and genetic instability.22,26,45,46 Female workers lie on the asbestos mattresses they have produced at a Lancashire factory, United Kingdom, September 1918 The speed of industrial development is far out-stripping the Photo credit: © Imperial War Museum (Q 28250) pace of regulatory development. In the absence of long-term monitoring and scientific information of the many aspects In 1982, a TV documentary, Alice, a Fight for Life, featured of nanomaterial toxicity and toxicology, specific regulations Alice Jefferson, a 47-year-old woman who contracted have been slow to emerge, despite mounting indications of mesothelioma, a fatal form of cancer, from working for a few potential exposure and risks.47 months at a local asbestos plant in the United Kingdom.20 The story of this Alice had an immediate impact on British Video: Are carbon nanotubes the next asbestos? public opinion. The government responded by introducing asbestos licensing regulations that lowered asbestos exposure limits. A voluntary labelling scheme soon followed. Pressure continued to build, and so did scientific evidence on the mesothelioma epidemic due to past exposure to asbestos.41

It took until 1999 for all types of asbestos to be banned in the United Kingdom: 101 years after evidence of harm had begun to accumulate and thousands of people had died of asbestosis or related . Today efforts are still made to minimize the risk of asbestos exposure to workers engaged in renovation and maintenance of buildings containing asbestos.42

The question is, “What lessons can we learn from the century of struggle to understand and address the deadly dangers posed by exposure to asbestos when managing and assuring the safety of nanomaterials in the future?”

Video link: https://www.youtube.com/watch?v=6L7xXgWcbrQ © Museum of Life and Science Photo credit: Geoff Hutchison, licensed under CC BY 2.0

30 As in the case for asbestos, the first people exposed to nanomaterials are workers. The first few studies conducted in the late 1990s and early 2000s to assess occupational exposure to carbon nanotubes paved the way for further workplace investigations, and later the establishment of a first ISO-guideline on characterizing occupational nanoaerosol exposures in 2007.48,49

Based on studies of animals exposed to carbon nanotubes and carbon nanofibres, the US National Institute for Occupational Safety and Health considers findings such as lung inflammation, and fibrosis in subject animals to be significant enough to warrant action to set a recommended exposure limit.22 The Organisation for Economic Co-operation and Development undertook multi-year programmes to generate toxicological data on a variety of nanomaterials to amend existing test guidelines for manufacturers.50

Because of the breadth of applications, regulatory bodies Carbon-graphene hierarchical core shell nanofibres Photo credit: Ranjith Shanmugam/ ZEISS Microscopy, licensed under CC BY-NC-ND 2.0 need to rely on existing regulations governing the areas of chemicals, pharmaceuticals, cosmetics, food, pollution, wastes and labelling to seek provisions for nanomaterials.51 are one of its emerging policy issues. It works with However, there are also challenges in applying existing governments and international stakeholders to facilitate regulatory frameworks to nanosized materials.47 For instance, information exchange on and engineered the reduction in size of a material may not initiate any need to nanomaterials and to develop internationally applicable revise the existing regulations or legislation if the nanosized technical and legal guidance for the sound management of and bulk materials are of the same chemical substance. manufactured nanomaterials.54 Or, some consumer products are not subject to safety requirements and can enter the market without being tested. When working with new technologies, regulatory bodies are confronted with a combination of promise, risk and In the European Union, the Regulation on Registration, uncertainty.55 Expanding the research, production and Evaluation, Authorisation and Restriction of Chemicals use of engineered nanomaterials across the world will (REACH) is used to ensure the human health and need transformative policies to encourage innovation environmental safety of any chemical substance to be and industrial applications of , and more manufactured and marketed in the EU. Companies need to critically, iterative and responsive regulatory frameworks that register the chemical substances they intend to manufacture apply the precautionary principle to assure safety and non- and trade, and, based on REACH’s specific guidelines, polluting outcomes. The world cannot afford to ignore the demonstrate how the risks associated with the substances can lessons of the past about risks and damages to human health be managed for human health and environmental safety.52,53 and the environment when responding to the promising opportunities created by new materials. At the global level, under the policy framework of the Strategic Approach to International Chemicals Management

(SAICM) administered by UN Environment, nanomaterials REPORT 2017 FRONTIERS ENVIRONMENT UN

31 NANOMATERIALS: APPLYING THE PRECAUTIONARY PRINCIPLE

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